左旋异松蒎酮的合成

研究了以(－)-α-蒎烯为原料合成(－)-异松蒎酮的反应. 以四氢呋喃为溶剂, 硼氢化钠与三氟化硼乙醚溶液生成的硼烷不经分离直接与α-蒎烯发生反马氏加成反应, 生成二异松蒎烷基硼; 采用四水合过硼酸钠或NaOH-H₂O₂氧化硼氢化物得到(＋)-异松蒎醇, 产率为89.5%, 纯度97.4%, 熔点为55～56 ℃, 比旋光度 ＋28.31 (c 5.55, CH₃OH). 以钒磷氧化物为催化剂、双氧水作氧化剂, 将(＋)-异松蒎醇氧化得到(－)-异松蒎酮, 产率88% 以上, 纯度96.0%, 比旋光度为 －10.58 (c 5.51, CH₃OH). 采用IR, MS, ¹H NMR, ¹³C NMR等对(＋)-异松蒎醇和(－)-异松蒎酮结构进行了表征.

Synthesis of (-)-Isopinocamphone

Synthesis of (－)-isopinocamphone was carried out using (－)-α-pinene as the starting material. Borane obtained from the reaction of NaBH₄ and BF₃?(C₂H₅)₂O without purification was directly re-acted with α-pinene in THF to obtain diisopinocampheylborane, which was further oxidized with so-dium perborate tetrahydrate to afford isopinocampheol as white solids, in a yield 89.5%, purity 97.4%, m.p. 55～56 ℃, ＋28.31 (c 5.55, CH₃OH). Isopinocamphone was prepared by oxidiz-ing isopinocampheol with hydrogen peroxide under catalysis of vanadium phosphorus oxide, in a yield over 88%, purity 96.0%, －10.58 (c 5.51, CH₃OH). The structures of isopinocampheol and isopinocamphone were determined by IR, ¹H NMR, ¹³C NMR and MS spec-tra.